Polymers of Intrinsic Microporosity Containing Trifluoromethyl and Phenylsulfone Groups as Materials for Membrane Gas Separation

Abstract

/npsi/ctrl?action=rtdoc&an=8934289&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=8934289&lang=frAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma801858dMacromolecules, 41, 24, pp. 9656-9662, 2008 Polymers of intrinsic microporosity containing trifluoromethyl and phenylsulfone groups as materials for membrane gas separation Du, Naiying; Robertson, Gilles; Song, Jingshe; Pinnau, Ingo; Thomas, Sylvie; Guiver, Michael Process and EnVironmental Technology, National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada, and Membrane Technology and Research Inc., 1360 Willow Road, Suite 103, Menlo Park, California 94025-1516 ReceiVed August 14, 2008 ReVised Manuscript ReceiVed October 14, 2008 ABSTRACT: A series of ladder copolymers and a homopolymer were synthesized via aromatic nucleophilic substitution polycondensation of 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethylspirobisindane with tetrafluoroterephthalonitrile and a new monomer heptafluoro-p-tolylphenylsulfone as potential materials for membrane gas separation. Ladder polymers of this type comprising rigid and contorted chain structure have been commonly referred to as polymers of intrinsic microporosity (PIM) on account of their extraordinarily high fractional free volumes (FFV) and high gas permeability (P). The PIM polymer series of the present study was prepared in high molecular weight and low molecular weight distribution, using new experimental conditions of short reaction times and a high temperature of 160°C. Polymer chain d-spacing was investigated using wide-angle X-ray diffraction. Polymer free volume was calculated from the polymer density and specific van der Waals volume. Gas permeabilities for oxygen and carbon dioxide decreased with increasing content of the trifluoromethylphenylsulfone versus the dinitrile monomer within the copolymer, while the selectivities of gases against nitrogen increased. The pendent phenylsulfone groups likely reside within the interchain free volume of the rigid and contorted ladder polymer, acting to reduce gas permeability and increase selectivity, though with no overall loss of performance relative the Robeson upper bound. Evidence for this is a reduction in d-spacing and fractional free volume with increasing content of the trifluoromethylphenylsulfone versus the dinitrile monomer in the copolymer series. The relationship between the gas permeabilit...

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

“…higher O 2 and CO 2 permeability is gained at the cost of lower selectivity and vice versa. In addition, the value of the annealed PIM-1 A was almost the same as the PIM-1 Ã and half the values of PIM-1 typically reported before, [8] but coupled with a corresponding increase in selectivity (Figure 1). An experimentally observed upper bound plot for C 3 H 6 / C 3 H 8 separation, constructed using available literature data, was reported previously.…”

High-Performance Carboxylated Polymers of Intrinsic Microporosity (PIMs) with Tunable Gas Transport Properties

“…In the present work, the PIM-1 starting material used for the hydrolysis experiments was gel-free and had high molecular weight (M n = 50 000, PDI = 2.0), which was obtained under an optimized polycondensation process. 20 Scheme 1 shows possible resulting repeat units derived from different degrees of hydrolysis. Polymer repeat units may contain zero, one, or two nitrile groups and correspondingly have two, one, or zero carboxylic acid groups.…”

“…20,21 Although several high-molecular-weight PIMs were recently prepared by polycondensation of new synthetic monomers, the present postmodification approach provides an alternative route to new PIM materials. In the present work, we report details of a simple postmodification hydrolysis reaction, which converts the nitrile groups in PIM-1 to carboxyl groups, providing structurally new PIM materials.…”

Gas transport behavior of mixed-matrix membranes composed of silica nanoparticles in a polymer of intrinsic microporosity (PIM-1)

“…Among these novel materials, PIM-1, containing the contorted spirobisindane unit, has attracted the most attention due to its relative ease of synthesizing high molecular weight polymer and the combination of outstanding permeability with moderate selectivity, especially for O 2 /N 2 and CO 2 /CH 4 pairs, which overcome the upper bound trade-off proposed by Robeson [18,19]. Since the initial reports of Budd et al and McKeown et al, structurally new PIMs and additional data on PIM-1 have appeared [20][21][22][23][24][25].…”